Adducts of bis-(2-pyridyl-1-oxide) disulfide with alkaline earth metal salts

ABSTRACT

This invention pertains to adducts of bis-(2-pyridyl-1-oxide) disulfide with alkaline earth metal salts, the method of their preparation and formulations containing such adducts.

Elite Sates Weisse et al.

atent I 1 June 18, 1974 ADDUCTS OF BIS-(Z-PYRIDYL-l-OXIDE) DISULFIDEWITH ALKALINE EARTH METAL SALTS [75] Inventors: Guenther K. Weisse,Northford;

Haywood Hooks, Jr., West Haven; Gene A. Hyde,.Hamden; Samuel 1. Trotz,Orange, all of Conn.

[73] Assignee: Olin Corporation, New Haven,

Conn.

[22] Filed: Oct. 18, 1971 [21] App]. No.: 190,382

[52] U.S. Cl 260/294.8 J, 252/106, 424/70, 424/263 [51] int. Cl C07d31/48 Primary ExaminerHenry R. Jiles Assistant ExaminerMildred A. M.Crowder Attorney, Agent, or Firm-Eugene Zagarella, Jr.

[ ABSTRACT This invention pertains to adducts of bis-(Z-pyridyl-loxide)disulfide with alkaline earth metal salts, the method of theirpreparation and formulations containing such adducts.

6 Claims, No Drawings ADDUCTS OF BIS-( 2-PYRIDYL-l-OXIDE) DISULFIDE WITHALKALINE EARTH METAL SALTS This invention relates to adducts of bis-(Z-pyridyl-loxide) disulfide and derivatives thereof and their method ofpreparation. More particularly, this invention relates to alkaline earthmetal salt adducts of the aforementioned disulfide compounds havingenhanced biocidal properties and to formulations containing suchadducts.

Bis-( 2pyridyl-l-oxide) disulfide (also referred to as2,2-dithiodipyridine-l,l'-dioxide) and various derivatives thereof havebeen previously disclosed in the literature. For example, U.S. Pat. No.2,742,476 discloses bis-(2-pyridyl-l-oxide) disulfide and lower alkylsubstituted derivatives thereof. US. Pat. No. 3,027,371 disclosesmolybdate derivatives, U.S. Pat. No. 3,027,372 discloses stannouschloride derivatives, and US. Pat. No. 3,346,578 discloses stannousfluoride derivatives of bis-(2-pyridyl-l-oxide) disulfide and each referto the antifungal and antibacterial properties of said derivatives. Inaddition to the above-noted disulfide compounds, many other compoundshave been used as biocides in various type preparations. However, mostcompounds are often characterized by one or more undesirable propertiessuch as l) insolubility or low solubility in water making them unusablein clear type formulations, 2) irritating to skin, 3) unpleasant odor,4) unstable under desired use conditions, e.g., at a pH greater thanabout 5. I

Now it has been found that adducts having a broad range of biocidalactivity can be provided according to this invention. More specifically,these adducts have the formula:

5 4 )2 l (I) wherein M is an alkaline earth metal, Y is the anion of aninorganic or organic acid and t is either 1 or 2. More particularly, theadducts (l) contain an alkaline earth metal (M) selected from the groupconsisting of calcium, magnesium, barium and strontium with calcium andmagnesium being preferred and the anion (Y) is selected from the groupconsisting of halides, sulfates, nitrates, chlorates and acetates withthe chorides and sulfates being preferred. More particularly preferredare the adducts of calcium chloride (CaCl or magnesium sulfate (MgSOAlso included in the adducts of this invention are hydrates of theaforementioned compounds, i.e., adducts including nH O groups where n isan integer of to 10. Additionally, the adducts (I) may contain one ormore substituents on either or both pyridine ring structures such asalkyls, halogens and alkoxy' groups. Reference to the adducts (I) in thespecification and claims is intended to include compounds con-- tainingsuch substituents. It is further noted that (C l-l.,NOS) as used in (I)above and throughout the specification and claims representsbis-(Z-pyridyl-loxide) disulfide and has the structural formula shownThe adducts (I) of this invention are prepared by reacting a selectedalkaline earth metal salt with bis-(2- Plt d lr xidehlisu fi or d rivstx 9 .n. h

presence of an inert solvent. More particularly, the inert solvent usedcan be an organic alcohol, preferably a lower alkanol of l to 4 carbonatoms and more preferably an alkanol of 2 to 4 carbon atoms. Mixtures ofsuch alkanols with water or other solvents may also be used if desired.The reaction mixture is generally maintained at a pH of about 1 to about8 and preferably from about 2 to about 5. The amounts of alkaline earthmetal salt and bis-(2-pyridyl-l-oxide) disulfide which are utilized canbe varied with a molar ratio of about 0.511 to about 2:1 of salt todisulfide being most generally used. Preferably, the amount used will beequimolar or have a slight excess of the alkaline earth metal salt.

The adducts (I) of this invention are useful as antimicrobial agentsbecause they exhibit high biological activity against a broad spectrumof microorganisms. Additionally, these adducts have been shown to besubstantive to calf skin, i.e., the property of remaining on the skinand retaining biocidal activity over a period of time after washing andrinsing of the skin. It is further noted that these adducts have thedesirable characteristic of being soluble in water and surfactantsolutions, thus, they may be used in a wide variety of cosmeticpreparations such as hair shampoos, hair dressings, hair preparations,anti-dandruff preparations, wave sets, lotions, creams, etc.-Moreparticularly, because of the desirable high solubility of the adducts(I) in aqueous solutions, they may be used in many clear typeformulations such as clear hair shampoos.

While a wide variety of cosmetic formultaions may be used a typicalformulation for a hair shampoo would include from about 10 to aboutpercent of a synthetic detergent; from 0 to about l0 percent of a foambuilder; from O to about 5 percent of a viscosity control agent; fromabout 0.000l to about 10 percent of the adducts of this invention (1);from 0 to about 15 percent of other ingredients well known to thoseskilled in the art, such as conditioners, pH control agents, colors,perfumes, clarifying agents, finishing agents, sequestering agent,protein derivatives, etc. and the balance of the formulation beingwater, more particularly from 0 to about 89 percent. The above percentsare on a weight basis.

In the above hair shampoo compositions the synthetic detergent may beselected from one or more detergents found in the classes known asanionic, cationic, non-ionic and amphoteric detergents.

Anionic detergents which are useful include alkyl aryl sulfonates, alkylglyceryl ether sulfonates, alkyl sulfates, long chain (fatty) alcoholsulfates, alkyl monoglyceride sulfates or sulfonates, alkyl polyethoxyether sulfates, acyl sarcosinates, acyl esters of isothionates, acylN-methyl taurides, alkyl benzene sulfonates, and alkyl phenol polyethoxysulfonates. In these compounds the alkyl and acyl groups, respectively,generally contain from 10 to 20 carbon atoms. They are used in the formof water-soluble salts, the sodium potassium, ammonium, andalkanol-ammonium salts, for example. Specific examples are sodium laurylsulfate, potassium N-methyl lauroyl tauride, and triethanolamine dodecylbenzene sulfonate.

Suitable examples of cationic detergents are dilauryldimethyl ammoniumchloride, diisobutyl phenoxy ethoxy ethyl dimethylbenzyl ammoniumchloride, cetyl trimethyl ammonium bromide, N-cetyl pyridinium bromideand benzethonium chloride, which are classed as quaternary ammoniumsalts.

Suitable examples of non-ionic detergents include alkoxy (ethyleneoxy)ethanol, polyethylene glycol 400 distearate, fatty acid amines with2-200 moles of ethylene oxide, sorbitan monolaurate, polyoxyethylene 4sorbitan monostearate and polyoxyethylene 2 oleyl ether.

Suitable exmples of amphoteric detergents are alkyl beta-iminodipropionates, and alkyl beta-amino propionates, where the alkyl group,generally contains 10 to 20 carbon atoms, N-lauryl betaine and basicquaternary ammonium compounds derived from 2-alkylsubstitutedimidazoline.

Further examples of useful synthetic detergents may be found inSynthetic Detergents" by A. Davidsohn and B. M. Milwidsky, Leonard Hill,London, 1967.

Typical foam builders useful in the above-identified shampoos includealkanolamides, such as lauroyl ethanolamide, and lauroyl diethanolamide.Typical viscosity control agents include natural gums, e.g., gumtragacanth; synthetic gums, e.g., carboxymethyl cellulose; syntheticpolymers, e.g., polyvinyl pyrrolidone; and inorganic salts.

A typical hair dressing formulation would include from 10 to about 50percent of a grooming agent; from to about 40 percent of a solubilizingagent; from 0 to about 40 percent of an emollient; from about 0.0001 toabout percent of the adducts of this invention (1); from about 0 toabout percent of other ingredients well known to those skilled in theart, such as filmforming agents, viscosity control agents, pH controlagents, colors, perfumes, etc. and the balance of the formulation beingwater, more particularly from 0 to about 89 percent. The above percentsbeing on a weight basis.

In the above hair dressing formulations, typical grooming agents includee.g., mineral oil, castor oil, isopropyl myristate, and oleyl alcohol.Typical solubilizing agents include ethanol and propylene glycol.Typical emollients include lanolin and glycerol.

The adducts of this invention (1) may be incorporated into a formulationin any amount capable of giving the desired biocidal effect andgenerally from about 0.0001 percent to about 10 percent by weight, basedon the total weight of the formulation, will be used. Preferably fromabout 0.1 to about 3 percent by weight and more preferably from about0.25 to about 2 percent of said adducts (I) are used. However, greateror lesser amounts may be employed, if desired.

in addition to using the adducts of this invention (1) in the variouscosmetic formulations, it was found that incorporation of the individualingredients which make up the adducts, i.e., the alkaline earth metalsalts and bis-( 2-pyridyl-l-oxide) disulfide, also resulted in theformation of clear compositions having effective biocidal activity. Theamounts used may vary from about 0.1 to 10 moles of selected alkalineearth metal salt per mole of selected bis-(2-pyridyl-l-oxide) disulfideand preferably from about 0.5 to about 3. On a weight basis the amountof selected alkaline earth metal salt may vary from about 0.4 to about85 and preferably from about 15 to about 60 percent by weight based onthe total amount of salt and disulfide used. The total concentration ofthe alkaline earth salt plus bis-(2-pyridyll-oxide) disulfide mixturecan be varied from about 0.1 to about 15 percent and preferably fromabout 0.3 to about 2 percent by weight, based on the total weight of theformulation.

The formulations noted above are merely exemplary of the many cosmeticand other preparations in which the adducts of this invention may beused. Many other cosmetic formulations which may be used can be found inCosmetics Science and Technology by Edward Sagarun, lntersciencePublishers, 1957; US. Pat. No. 3,236,733 with Karsten, Taylor and Parranas inventors and Canadian Patent 1,202,716 with Gerstein, Perlburg andSchwartz as inventors.

The following examples will further illustrate the method of preparingthe adducts (1) and some of the formulations containing such adducts andthe components thereof but are not to be considered as limiting thescope of this invention.

EXAMPLE 1 A l-liter, 3-neck flask equipped with mechanical stirring, areflux condenser and thermometer was charged with 33.3 g. (0.3 mole) ofcalcium chloride and 400 ml. of ethanol. The pH was adjusted to about2.0 with the addition of hydrochloric acid. Stirring briefly resulted inclear solution at about 50C. to which was added, in portions, 50.4 g.(0.2 mole) of bis-(2-pyridyl-l-oxide) disulfide during a period of tenminutes. The resulting slurry was stirred for an additional 3.5 hours atreflux. The reaction mixture was cooled to about 45 to 50C. and thesolid product was filtered off, dried over P 0 at reduced pressure, andwashed with ethanol. The yield was 67 g. (93 percent) of white,microcrystalline powder, showing a decomposition beginning at around265C. and darkening appreciably above 300C.

Elemental Analysis: Calcd for: C,.,H,,O N,S,Cl Ca: C, 33.0: H, 2.2; N.7.72; CI, 19.5;

Found: C, 32.84; H, 2.14; N, 7.73; Cl, 19.83; Ca, l0.79.

X-ray analysis indicated that the powder diffraction pattern did notcorrespond to either of the reactants or other known standard patternsand is believed to be characteristic of this new composition. infraredanalysis confirmed this result.

EXAMPLE 2 A l-liter, 3-neck flask equipped with thermometer andrefluxing condenser, was charged with 26 g. (0.216 mole) of MgSO,dissolved in 100 ml. of H 0, and the pH adjusted to 2.0 with H Then 50.2g. (0.2 mole) of bis-(2-pyridyl-l-oxide) disulfide was added portionwisewith stirring within 5 min. The resulting slurry was stirred and heatedat 6070C. for 0.5 hour. To the resulting slurry was added siowly 300 ml.of methyl alcohol during continued stirring and heating. The mixture wasthen heated and stirred at reflux for an additional 3.5 hours, followingwhich the reaction mixture was allowed to cool to 3035C. with stirring.The solid product was filtered off, washed by slurrying two times, eachin 500 m1. of methyl alcohol (with stirring) at 4550C., and collected onfilter. The white solid was dried at 6570C. under reduced pressure toyield 88.8 g. (0.19 mole), 99 percent yield, m.p. 210-212C.(decomposition).

35.0 g. of the above dried sample was subjected to azeotropicdistillation with xylene to yield 4.5 g. of H 0 equivalent to 12.9percent of the sample. The theoretical yield of B 0 was 12.7 percentbased on a formula of C l-l O N S Mg-3H O.

. it to be (C H NOS) Elemental Analysis:

Calcd for: C H O N,S Mg-3H O: C, 28.2; H, 3.3; N. 6,6;

S, 22.5; Mg. 5.7. Found: C. 28.1;1-1, 3.2; N, 6.5; S, 22.1; Mg, 5.7.

X-ray and infrared analyses confirmed this result.

EXAMPLE 3 The same procedure as in Example 1 was followed using 25.2 g.of bis-(2-pyridyl-1-oxide) disulfide and 16.2 g. of strontium chloride(SrCl A 30.8 g. product (95 percent yield) was obtained and analysesindicated it to be (C H NOS) -SrCl EXAMPLE 4 The same procedure as inExample 1 was followed using 25.2 g. of bis-(2-pyridyl-l-oxide)disulfide and 24.8 g. of strontium bromide (SrBr A 45.4 g. product (92percent yield) was obtained and analyses indicated it to be (C H NOS)'SrBr i amass The same procedure as in Example 1 was followed using 25.2g. of bis-(2-pyridyl-l-oxide) disulfide and 33.3 g. of barium bromide(BaBr A product of 57.9

g. (99 percent yield) was obtained and analyses indicated it to be (C HNOS) -BaBr The same procedure as in Example 1 was followed using 78 g.of bis-(2-pyridyl-1-oxide) disulfide and 56 g. of calcium nitrate Ca(NOA 123 g. product (92.5

percent yield) was obtained and analyses indicated it to be M0502.

EXAMPLE 7 The same procedure as in Example 1 was followed using 25.2 g.of bis-( 2-pyridyl-l-oxide) disulfide and-35 g. of barium chlorateBa(ClO )2 H 0. A 56 g. product (74 percent yield) was obtained andanalyses indicated Ba(ClO H O.

Several shampoo and hair dressing compositions were prepared containingthe formulations shown in Tables I and Il. Several examples showingthese formulations in combination with the adducts (l) of this inventionare described below.

EXAMPLE 8 A clear hair shampoo composition having the followingformulation was prepared:

Percent by Weight Hair shampoo composition No. l l

(C FLNOSL'CaCI The pH of the above formulation was adjusted to 7.2. Thisformulation was tested for biocidal activity against P. ovale using invitro serial dilution analysis. This method of analysis involves addingthe test compound to several tubes containing inoculated broths indifferent concentration so that a range of concentrations isestablished. The tubes are mixed and incubated at appropriatetemperatures (37C. for most bacteria and yeasts, 28C. for molds). After24 hours incubation, the number of organisms remaining in the inoculatedtubes of.

TABLE I Shampoo Compositions Code No. ingredients 1 2 3 4 5 6triethanolamine 35 lauryl sulfate sodium lauryl sulfate diethanolaminelauryl sulfate triethanolamine alkyl aryl sulfonate ammoniumethoxylauryl sulfate sodium lauryl ether sulfate sodium lanolin ethersulfate Duponol XL polyoxyethylene 4 Sorbitan-monoleate sulfatedvegetable oil alkanolamide 5 4 6 mineral oil glycerol Natrosol 250l-ll-ll Oleyl alcohol propylene glycol NaCl Miranol C 2M Cone:

water lngredients 7 8 9 Miranol C 2M Cone. water Anionic amphotericsurfactant of alcohol sulfate type z hydroxylethylether of cellulose al-ethoxyethionic acid-l ethionic acid-5-cocoylcyclo-imidinium hydroxide.disodium salt.

The pH of the above compositions was adjusted to 7.4 with HCl andperfume was added in a sufficient quantity to give desired effects.

TABLE II l;l air Dressing Compositions Code No.

Ingredients l3 14 glycerol 40.0 ethyl alcohol 40.0 Atlas G-l790 15.0water 20.0 85.0

' polyoxyethylene 20 lanolin derivative The pH of the above compositionswas adjusted to 7.4 with HCl and perfume was added in a sufficientquantity to give desired effects.

bacteria or yeast are determined by routine agar plating st qd t ou h, e.ussof. C ts Electronic Particle Counter (samples inoculated with moldsare measured after 7 days using agar plating methods). The minimallethal concentration (M.L.C.) is recorded as the lowest concentration ofa compound which completely destroys population of organisms within agiven limit of time. The minimal lethal concentration (M.L.C.) was foundto be 4.5 ppm. and the same formulation without the adduct added had aM.L.C. of 150 ppm. (for P. ovale).

The substantive properties of the tested formulations were determined bymeans of agar plate zone of inhibition testing. This testing involvesplacing discs (-l 2.5 mm.) of treated untanned calf skin upon thesurface of agar plates previously seeded with test organisms. Uponincubation at the optimum temperature, the activity of the test compoundis reflected by zones of nogrowth beneath and/or surrounding the testdiscs, i.e., the zone of inhibition.

Substantivity to calf skin was determined for a number of organisms withthe following results:

Organism lnhib.Zone-Diameter (mm.)

Salmonella typhimurium 34 Salmonella enteritidis 35 Escherichia coli9637 38 Escherichia coli 10536 l Staphylococcus aureus 32 Klebsiellapneumoniae 23 Pitysporium ovale l 8 M EXAMPLE a A clear hair shampoocomposition having the following formulation was prepared:

Percent by Weight Hair shampoo composition No. ll 98.5 (c5H.Nos),-Mso.sH,o 100.0

The pH of the above formulation was adjusted to 7.2. The biocidalactivity for P. ovale was found to be 1.5 ppm. as compared with 150 ppm.for a sample of the formulation without the magnesium sulfate adduct.

Substantivity to calf skin was determined for a number of organisms withthe following results:

Organism lnhib.Zone-Diameter (mm.)

Salmonella typhimurium 33 Salmonella enteritidis 33 Escherichia coli9637 33 Escherichia coli 10536 17 Staphylococcus aureus 3l Klebsiellapneumoniae 20 Pitysporium ovale l 3 EXAMPLE 10 A clear hair shampoocomposition having the following formulation was prepared:

Percent by Weight Hair shampoo composition No. 1 99.5 c.H.N0s),-M so,-3Ho i000 The pH of the formulation was adjusted to 7.3. Substantivity tocalf skin was determined to be 33 mm. for S. aureus as compared with 30mm. for a formulation without the adduct.

EXAMPLE 1 l A clear hair shampoo composition having the followingformulation was prepared:

Percent by Weight Hair shampoo composition No. 1 99.5 (C,,H NOS),-CaCl,(1.5 100.0

The pH of the above formulation was adjusted to 7.2. The biocidalactivity for P. ovale was found to be 0.25 ppm. as compared with ppm.for a sample of the formulation without the calcium chloride adduct.

EXAMPLE 12 A clear hair shampoo composition having the followingformulation was prepared:

Percent by Weight Hair shampoo composition No. 2 99.0 (C H N 0S CaCl L01000 The pH of this formulation was adjusted to 7.2. The biocidalactivity for P. ovale was found to be 0.12 ppm. as compared to 150 ppm.for a sample of the formulation without the calcium chloride adduct.Substantivity to calf skin was determined to be 38 mm. for S. aureus ascompared to 24 mm. for a formulation without the adduct.

EXAMPLE 13 A clear hair shampoo composition having the followingformulation was prepared:

Percent by Weight Hair shampoo composition No. 2 99.0 (ca-mos ),'MgSO-3H,0 L0 100.0

The pH of the above formulation was adjusted to 6.2

9 l Substantivity to calf skin was determined to be 28 EXAMPLE 18 I23 a;ai z to 24 for a formu' A clear hair shampoo composition having thefollowi e a ing fe twes Prepares; EXAMPLE 14 Percent by A clear hairshampoo composition having the follow- Weight mg formulatlon wasprepared: Hair shampoo composition No. 5 98.5 (C5H4NOS -MgSO -3H Q l100.0 Percent by I we'ght The pH of this formulation was adjusted to7.3. Sub: Hair Shampoo composition 3 98's stantivlty to calf skin wasdetermined to be 36 mm. for (c nntosncacl S. aureus as compared to 28mm. for a sample of the 100-0 formulation without the adduct.

The pH of this formulation was adjusted to 7.3. The EXAMPLE l9 biocidalactivity for P. ovale was found to be 0.25 ppm. A clear hair shampoocomposition having the f ll as compared with 150 ppm. for a sample ofthe fori f l ti was prepared; mulation without the adduct. I

EXAMPLE 15 Paiegttnby A clear hair shampoo composition having thefollow- Hair Shampoo composition 6 990 ing formulation was prepared: (CH NOS) -CaCl I000 Percent by The pH of this formulation was ad usted to6.2. The Weigh biocidal activity for P. ovale was found to be 0.25 ppm.Ha shampoo composition No 4 985 as compared with 150 ppm. for a sampleof the for- (C I-L NOSh-CaCI 1.5 mulation without the adduct.

EXAMPLE 20 The pH of the formulation as adjust t0 The A clear hairshampoo composition having the followbiocidal activity for P. ovale wasfound to be 0.5 ppm. ing formulation was prepared: as compared with 150ppm. for a sample of the formulation without the adduct. Percent byWeight EXAMPLE 16 Hair shampoo composition No. 7 99.2 A clear hairshampoo composition having the follow- (CHNOSMCQCIZ ing formulation wasprepared: 40

The pH of this formulation was adjusted to 6.5. Substantivity tocalfskin was determined to be 34 mm. for Percent by we S. aureus.

Hair shampoo composition No. 4 98.5 EXAMPLE 2] (CSmNOSHMgSOflHzO [F83 Aclear hair shampoo composition having the following formulation wasprepared:

The pH of this formulation was adjusted to 7.3. Substantivity to calfskin was determined to be 32 mm. for Percent by S. aureus as compared to28 mm. for a formulation weigh Without th adduct- M H Hair shampoocomposition No. 8 98.5 I (C H NOS) -CaCl -5. 100.0

EXAMPLE 17 A clear hair shampoo composition having the followingformulation was prepared:

I The pH of the above formulation was adjusted to 6.2.

The biocidal activity for P. ovale was found to be 0.5 ppm. as comparedwith 50 ppm. for a sample of the formulation without the adduct.

i ga EXAMPLE 22 Hair Shampoo composmun N0. 5 99-25 A clear ha r shampoocomposition having the follow- (CQHNOSHCEICIT 0,75 mg formulation wasprepared:

The pH of this formulation was adjusted to 7.2. The ig 53? biocidalactivity for P. ovale was found to be 0.5 ppm. as compared with ppm. fora sample of this for- Hair l comvosilim 8 f;

. c N i 50- H o mulation without the adduct. OSMMg 1 100.0

The pH of this formulation was adjusted to 7.3. Substantivity to calfskin was determined to be 39 mm. for S. aureus as compared to 30 mm. fora sample of the formulation without the adduct.

5 EXAMPLE 23 A clear hair shampoo composition having the followingformulation was prepared:

Percent by Weight Hair shampoo composition No. 9 98.5 c ii,Nos) -Cacl,11.

The pH of this formulation was adjusted to 7.2. The biocidal activityfor P. ovale was found to be 0.2 ppm. as compared with 50 ppm. for asample of the formulation without the adduct.

EXAMPLE 24 A clear hair shampoo composition having the followingformulation was prepared: 25

Percent by Weight Hair shampoo composition No. 9 99.0 (C5H.NOS )z'Mso.-3H,o 100.0

The pH of this formulation was adjusted to 6.2. Substantivity to calfskin was determined to be 32 mm. for

35 S. aureus as compared to 28 mm. for a sample of the formulationwithout the adduct.

EXAMPLE 25 A clear hair shampoo composition having the followingformulation was prepared:

Percent by Weight Hair shampoo composition No. 10 99.0 (cnmwosi -caci iThe pH of this formulation was adjusted to 7.0. The 5Q blocidal activityfor P. ovale was found to be 1.5 ppm. as compared with ppm. for a sampleof the formulation without the adduct.

EXAMPLE 26 A clear hair shampoo composition having the followingformulation was prepared:

Percent by Weight Hair shampoo composition No. 10 99.5 (C H NOS) 'MgSO3H O 100.0

The pH of this formulation was adjusted to 7.3. Substantivity of calfskin was detennined to be 31 mm. for S. aureus.

EXAMPLE 27 A clear hair dressing composition having the followingformulation was prepared:

Percent by Weight Hair dressing composition No. 13 99.5 (c imiosycaci100.0

The pH of this formulation was adjusted to 6.2. The biocidai activityagainst P. ovale was found to be 0.15 ppm. as compared with 50 ppm. fora sample of the formulation without the adduct.

EXAMPLE 28 A clear hair dressing composition having the followingformulation was prepared:

Percent by Weight Hair dressing composition No. 14 99.5 (C H NOS),CaCl,100.0

EXAMPLE 29 A clear antiseptic and disinfectant composition having thefollowing formulation was prepared:

Percent by Weight Water 98.5 (C l-LNOS CaCl, I 100.0

The pH of this formulation was adjusted to 7.2. The biocidal activityfor this formuiation was determined for several organisms with theresults as indicated be low:

Minimal Lethal Organism Concentration ppm.

Aspergillus niger Penicillium vermiculatum Epidermophyton floccosum 3Trichophyton mentagrophytes 3 Candida albicans 6 Saccharomycescerevisiae 1.5 Staphylococcus aureus 25 Baciilus subtilis 60 Pseudomonasaeruginosa 1 15 Escherichia coli 60 EXAMPLE 30 A clear antiseptic anddisinfectant composition having the following formulation was prepared:

i "War cium chloride resulted in inhibition zones of 23, 30 and mg 18mm. respectively.

Water 98.5 V. W... (C H NS),*MgSO.-3H,O

.- EXAMPLE 33 The pH of this formulation was adjusted to The A clearhair shampoo composition having the followbiocidal activity forseveralorganisms was determined mg formulatlon was Prepared: with thefollowing results:

10 Percent by Weight Minimal Lethal I Organism Concemrallon PP Hairshampoo composition No. 12 99.49 H Bis-(2-pyridyl-l-oxide) disulfide0.35 Aspergillus niger l5 Magnesium sulfate Penicillium vermiculatum 15100,00 Epidermophyton floccosum 3 l 5 Tricho h ton menta ro h tes 4.5 YCandid: Zlbicans g p y 6 The pH of this formulation was ad usted to 7.3.The s f y cerevisiae substantivity to calf skin was determined forseveral org g if fgfiz 55 ganisms with the following results:Pseudomonas aeruginosa 120 Escherichia coli 55 0 Organism lnhib. Zonediameter (mm.)

Pseudomonas aeruginosa 3] EXAMPLE 31 Staphylococcus aureus 30 Salmonellatyphimurium 22 A clear hair shampoo composition having the follow- 2 5 gformulation was Prepared: The same formulation without the disulfide andmagnesium sulfate resulted in inhibition zones of 18, 25 and Percent by18 mm. respectively.

Weight A .c wk Hair shampoo composition No. 2 99.00Bis-(2-pyridyl-1-oxide) disulfide 8.68 EXAMPLE 34 Magnes'um sulfate Aclear hair shampoo composition having the following formulation wasprepared:

The pH of this formulation was adjusted to 6.3. The 3 5 substantivity tocalf skin was determined for several or- Percent by ganisms with thefollowing results: Weight Hair shampoo composition No. 12 99.49 B'- 2- dl-ld d. Organism lflhlb. Zoncdiamcter (mm.) 40 f g g' g f sulfide 100.00Pseudomonas ucruginosa 15442 27 Staphylococcus aurcus 32 t Salmoncllatyphimurium 18 The pH of this formulation was ad usted to 6.8. The

substantivity to calf skin was determined for several organisms with thefollowing results: EX PLE 32 .c a.

A clear hair shampoo having the following formula- Organism lnhiblonediameter (mm.) non was prepared Pseudomonas aeruginosa 20 Staphylococcusaureus 26 Salmonella typhimurium 22 Percent by Weight Hair 2 990 i Thesame formulation without the disulfide and cal-Bis-(Z-pyridyl-1-oxide)disulfide 0.69

c ium chmride 0.31 cium chloride resulted in inhibition zones of 18, 25and 100-00 18 mm. respectively.

The pH of the formulation was adjusted to 7.2. The substantivity to calfskin was determined for several or- E AMPLE 35 gamsms with the followmgresults: 0 A clear antiseptic and disinfectant composition was preparedhaving the following formulation:

Organism lnhiblonc-diamctcr (mm.)

Pueudomonas acruginosa 15442 30 Percent by Staphylococcus aureus 36Weight Salmonella typhimurium 36 Water 98.50 Bis-(Z-pyridyl-l-oxide)disulfide 1.06 Calcium chloride 0.44

The same formulation without the disulfide and cal- 100.00

The pH of this formulation was adjusted to 6.3. The biocidal activityfor this formulation was detennined for several organisms with theresults as indicated below:

EXAMPLE 36 A clear antiseptic and disinfectant composition was preparedhaving the following formulation:

The pH of this formulation was adjusted to 6.3. The h qs qel SFYFY 9 t iu a es we s a i s several organisms with the results as indicated below:

Organism Minimal Lethal Conc. ppm.

Aspergillus niger l5 Penicillium vermiculatum l5 Epidermophytonfloccosum 3 Trichophyton mentagrophytes 6 Candida albicans 6Saccharomyces cerevisiae 1.5 Staphylococcus aureus 25 Bacillus subtilis7O Pseudomonas aeruginosa I50 Escherichia coli 50 What is claimed is:

1. An adduct of bis-(2-pyridyli -oxide) disulfide having the empiricalformula:

( sm h t and hydrates thereof, wherein M is an alkaline earth metalselected from the group consisting of calcium, magnesium, barium andstrontium; Y is an anion selected from the group consisting of halides,sulfates, nitrates, chlorates and acetates and t is either 1 or 2.

2. The adduct of claim 1 wherein M is calcium or magnesium.

3. The adduct of claim 2 wherein Y is chloride or sulfate.

4. The adduct of claim 3 wherein M is calcium, Y is chloride and t is 2.

5. The adduct of claim 3 wherein M is magnesium, Y is sulfate and t isl.

6. The adduct of claim 1 wherein the formula is selected from the groupconsisting of (C l-LNOS CaCl

2. The adduct of claim 1 wherein M is calcium or magnesium.
 3. Theadduct of claim 2 wherein Y is chloride or sulfate.
 4. The adduct ofclaim 3 wherein M is calcium, Y is chloride and t is
 2. 5. The adduct ofclaim 3 wherein M is magnesium, Y is sulfate and t is
 1. 6. The adductof claim 1 wherein the formula is selected from the group consisting of(C5H4NOS)2CaCl2, (C5H4NOS)2MgSO4 X not identical 3H2O, (C5H4NOS)2SrCl2,(C5H4NOS)2SrBr2, (C5H4NOS)2BaBr2, (C5H4NOS)2Ca(NO3)2 and(C5H4NOS)2Ba(ClO3)2 X H2O.